Photosensitve resin composition

ABSTRACT

A photosensitive resin composition comprises an alkali soluble acrylic resin, a photosensitizer containing a quinone diazide group, a solvent and if necessary a hardening agent containing epoxy groups, wherein said solvent is a mixture of propylene glycol monomethyl ether acetate and a solvent having smaller vapor pressure than that of propylene glycol monomethyl ether acetate at the normal temperature and the atmospheric pressure and said composition further contains a phenolic compound represented by general formula (I) below. The photosensitive resin composition can be used suitably as a material for forming an interlayer dielectric or a planarization film, etc. of semiconductor devices, flat panel displays or the like.  
                 
 
wherein R 1 , R 2 , R 3 , R 4 , R 5 , R 6  and R 7  represent independently H, a C 1-4  alkyl group or  
                 
whereupon each of m and n is independently an integer of 0 to 2, each of a, b, c, d, e, f, g and h is an integer of 0 to 5 satisfying a+b≦5, c+d≦5, e+f≦5 and g+h≦5, and i is an integer of 0 to 2.

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a photosensitive resin composition,further in detail to the photosensitive resin composition which issuitable for formation of an interlayer dielectric or a planarizationfilm for a semiconductor device, a flat panel display (FPD), and so on.

BACKGROUND ART

In the wide fields of manufacturing of a semiconductor integratedcircuits such as LSI or a display face of FPD, manufacturing of acircuit substrate for a thermal head and so on, photolithographytechnique has so far been employed for forming microelements orconducting fine processing. In the photolithography technique, apositive- or negative-working photosensitive resin composition is usedfor forming a resist pattern. In the recent years, a formation techniqueof an interlayer dielectric or a planarization film, which insulatesbetween wiring circuits in a semiconductor integrated circuit or an FPD,is being paid attention as new applications. Particularly a marketrequirement for a highly precise and fine technology is strong and thenit is said that a planarization film which is highly transparent andexcellent in dielectric property is an essential material in order toattain such highly precise and fine technology. Many studies are beingconducted for the photosensitive resin composition used for suchapplications and many patents are filed and made laid-open, for exampleJapanese Patent Publication Laid-open No. Hei7-248629, and JapanesePatent Publication Laid-open No. Hei8-262709. However the materialswhich were developed as being suitable for these interlayer dielectricand planarization film have less stability depending on time. Thereforea special care is required for a storage circumstance of the compositioncompared with a positive-working resist which is used for a fineprocessing commonly. Further when these compositions are used forformation of an FPD display face or manufacturing of a semiconductordevice, it is known that a coating property of the photosensitive resincomposition affects a display performance such as light unevenness ofthe FPD at the time of turning on light of the panel. Furthermore adevelopment residue often causes a defect of hole of the pattern, andconnecting failure of wires are taken place by this and would become acause of prevention of electricity conduction of metals. Because ofthis, a photosensitive resin composition, by which a pattern not onlyhaving a excellent dielectric property, a high heat resistance and agood stability depending on time but also having an improved coatingproperty and no development residue can be formed, is being required.

In order to respond this matter, the inventors of the present inventionproposed, in Japanese Patent Application No. 2001-389601, thephotosensitive resin composition by which a thin film having a goodinsulating property, heat-resistance, resolution and light transmissionproperty can be formed, and whose stability depending on time is goodeven if a hardening agent is added. In addition, heat-resistance of thefilm formed by using the photosensitive resin composition is furtherimproved. The photosensitive resin composition of Japanese PatentApplication No. 2001-389601 is a photosensitive resin compositioncomprising an alkali-soluble acrylic resin, a photosensitizer containinga quinone diazide group, a phenolic compound represented by the generalformula (I) described later, and if necessary a hardening agent havingepoxy groups. However development residue or a coating property of thephotosensitive resin composition is not satisfactory. Therefore theproblems still remain.

Referring to the situation described above, the objects of the presentinvention are to offer the photosensitive resin composition without theproblems described above.

It means that the object of the present invention is to offer aphotosensitive resin composition having a good stability depending ontime, an excellent insulation property, heat-resistance, and transparentproperty as well as a good coating property and no development residue,which can be preferably used for an interlayer dielectric or aplanarization film for an FPD's display face or a semiconductor device,and so on.

Further the object of the present invention is to offer a photosensitiveresin composition comprising an alkali-soluble acrylic resin, aphotosensitizer containing a quinone diazide group, a phenolic compoundrepresented by the general formula (I) described later and if necessarya hardening agent having epoxy groups, by which a pattern having a goodcoating property but no development residue can be formed.

DISCLOSURE OF THE INVENTION

As a result of eager study and examination, the present inventors foundthat the above described objects can be attained by using someparticular solvents as a solvent in a photosensitive resin compositioncomprising an alkali-soluble acrylic resin, a photosensitizer containinga quinone diazide group, a phenolic compound represented by the generalformula (I) described later, a solvent and if necessary a hardeningagent having epoxy groups, and reached to the present invention.

It means that the present invention relates to a photosensitive resincomposition which is characterized by comprising an acrylic resin as analkali-soluble resin, a mixture of propylene glycol monomethyl etheracetate and a solvent having smaller vapor pressure than that ofpropylene glycol monomethyl ether acetate at the normal temperature andthe atmospheric pressure as a solvent, and besides a phenolic compoundrepresented by the general formula (I) described below in thephotosensitive resin composition comprising an alkali-soluble resin, aphotosensitizer containing a quinone diazide group, a solvent, and ifnecessary a hardening agent having epoxy groups.

wherein R₁, R₂, R₃, R₄, R₅, R₆ and R₇ independently represent H, a C₁-C₄alkyl group or a group represented by the formula:

whereupon each of m and n is independently an integer of 0 to 2, each ofa, b, c, d, e, f, g and h is an integer of 0 to 5 satisfying a+b≦5,c+d≦5, e+f≦5 and g+h≦5, and i is an integer of 0 to 2.

As described above, the photosensitive resin composition of the presentinvention comprises an alkali-soluble resin, a photosensitizercontaining a quinone diazide group, a phenolic compound represented bythe general formula (I) described above, a solvent and if necessary ahardening agent containing epoxy groups. Since the solvent to be usedtakes a large characteristic in the present invention, theconstitutional compositions of the photosensitive resin composition ofthe present invention are now be explained in detail from the solvent inorder.

The solvent to be used in a photosensitive resin composition of thepresent invention needs to be a mixture of propylene glycol monomethylether acetate and a solvent having smaller vapor pressure than that ofpropylene glycol monomethyl ether acetate at the normal temperature andthe atmospheric pressure. The vapor pressure of propylene glycolmonomethyl ether acetate at the normal temperature (20° C.) and underthe atmospheric pressure (1013 hPa) is 3.5 mmHg. Solvents, the vaporpressure of which at the normal temperature and the atmospheric pressureis lower than that of propylene glycol monomethyl ether acetate, can beexemplified by dipropylene glycol n-butyl ether (0.06 mmHg),tripropylene glycol methyl ether (0.02 mmHg), propylene glycol phenylether (0.01 mmHg), propylene glycol n-butyl ether (0.6 mmHg),2-heptanone (2.1 mmHg), methyl-3-methoxy propionate (1.8 mmHg), methyl2-hydroxy propionate (0.3 mmHg), ethyl 2-hydroxy propionate (2.7 mmHg),butyl 2-hydroxy propionate (0.03 mmHg), ethylene glycol monoethyl etheracetate (1.1 mmHg), propylene glycol (0.08 mmHg), ethyl 3-ethoxypropionate (0.7 mmHg), and so on. These solvents can be used singly withpropylene glycol monomethyl ether acetate in a mixture or as a mixtureof two or more kinds thereof with propylene glycol monomethyl etheracetate in a mixture.

In the present invention, solvents so far being used as a solvent for aphotosensitive resin composition may be further used with the solventabove such as propylene glycol monoalkyl ethers, e.g. propylene glycolmonomethyl ether and propylene glycol monoethyl ether; propylene glycolmonoalkyl ether acetates, e.g. propylene glycol monomethyl ether acetateand propylene glycol monoethyl ether acetate; aromatic hydrocarbons,e.g. toluene and xylene; ketones, e.g. methyl ethyl ketone, 2-heptanone,and cyclohexanone; amides, e.g. N,N-dimethylacetamide andN-methylpyrrolidone; lactones, e.g. γ-butyrolactone; and so on. Thosesolvents can used in a mixture as far as the objects of the presentinvention cannot be spoiled.

As a solvent having smaller vapor pressure at the normal temperature andthe atmospheric pressure than that of propylene glycol monomethyl etheracetate to be used in a mixture with propylene glycol monomethyl etheracetate, ethyl 2-hydroxypropionate, propylene glycol n-butyl ether,propylene glycol are preferable, and ethyl 2-hydroxypropionate is morepreferable. A preferable mixing range of propylene glycol monomethylether acetate and the solvent, the vapor pressure of which at the normaltemperature and the atmospheric pressure is lower than that of propyleneglycol monomethyl ether acetate, is preferably 95:5 to 50:50, morepreferably 90:10 to 70:30.

In this connection the vapor pressure data of solvents can be referredto “Solvent Hand Book” published by Kodansya, “14102 Chemical Products”published by Kagaku Kogyo Nippoh Co., “MSDS data (Material Safety dataSheet)” provided by solvent manufacturers and so on.

As the alkali-soluble resin used in the photosensitive resin compositionof the present invention, acrylic resins are preferable. As the acrylicresins, alkali-soluble polyacrylic esters (a), alkali-solublepolymethacrylic esters (b), and alkali-soluble poly(acrylicester-co-methacrylic ester) containing at least one kind of acrylicesters and at least one kind of methacrylic esters as a constitutionalunit (c) can be exemplified. These acrylic resins can be used singly orin a mixture of two or more kinds thereof. As these acrylic resins,acrylic resins containing an organic acid monomer as a comonomer ispreferred in order to make the resin alkali-soluble, however a comonomerunit to give alkali-solubility to the resin is not limited in theorganic acid monomer.

As a monomer component which constitutes these polyacrylic esters,polymethacrylic esters, and poly(acrylic ester-co-methacrylic ester), anacrylic ester, a methacrylic ester, an organic acid monomer and othercopolymerizable monomers are raised.

As these monomer components which constitutes these polyacrylic esters,acrylic esters, methacrylic esters and organic acid monomers, onesillustrated below are preferred.

Acrylic Ester:

Methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate,n-hexyl acrylate, isopropyl acrylate, isobutyl acrylate, t-butylacrylate, cyclohexyl acrylate, benzyl acrylate, 2-chloroethyl acrylate,methyl-1-chloroacrylate, phenyl-α-bromoacrylate and so on.

Methacrylic Ester:

Methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, n-butylmethacrylate, n-hexyl methacrylate, isopropyl methacrylate, isobutylmethacrylate, t-butyl methacrylate, cyclohexyl methacrylate, benzylmethacrylate, phenyl methacrylate, 1-phenylethyl methacrylate,2-phenylethyl methacrylate, furfuryl methacrylate, diphenylmethylmethacrylate, pentachlorophenyl methacrylate, naphthyl methacrylate,iso-boronyl methacrylate, hydroxyethyl methacrylate, hydroxypropylmethacrylate, and so on.

Organic Acid Monomer:

Unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid,and crotonic acid; unsaturated dicarboxylic acids and their anhydridesuch as itaconic acid, maleic acid, fumaric acid, citraconic acid, andmetaconic acid; 2-acryloyl hydrogenphthalate, 2-acryloyloxypropylhydrogenphthalate, and so on.

Other copolymerizable monomers can be exemplified with maleic diesters,fumaric diesters, styrene and styrene derivatives, acrylonitrile,(meth)acrylamide, vinyl acetate, vinyl chloride, vinylidene chloride,and so on. These other copolymerizable monomers may be used if necessaryand its quantity shall be the quantity in the limit wherein the acrylicresins can attain the objects of the present invention.

A preferable acrylic resin of the present invention is a copolymercontaining a constitutional unit derived from alkyl (meth)acrylate and aconstitutional unit derived from (meth)acrylic acid, and more preferableone is the copolymer containing 5 to 30 mole-% of (meth)acrylic acid. Apreferable limit of weight average molecular weight as determined bypolystyrene standards of acrylic resins of the present invention is20,000 to 40,000, more preferably 25,000 to 30,000.

A photosensitizer having a quinone diazide group which is used in thephotosensitive resin composition of the present invention may be any oneif it is a photosensitizer having a quinone diazide group. Of thephotosensitizers, it is preferred that the one which is obtained byreacting a quinone diazide sulfonic halide such as a naphthoquinonediazide sulfonic chloride or a benzoquinone diazide sulfonic chloridewith a low or high molecular compound having a functional group which iscondensable with this acid halide. The functional group which iscondensable with acid halide here includes a hydroxyl group, an aminogroup, and so on and particularly a hydroxyl group is preferable. A lowmolecular compound containing a hydroxyl group includes the phenoliccompound represented by the general formula (I) described above. Thesephotosensitizers having a quinone diazide group are used usually at 1 to30 parts by weight relative to 100 parts by weight of a resin componentin a photosensitive resin composition of the present invention.

The photosensitive resin composition of the present invention furthercontains preferably the phenolic compound represented by theabove-described general formula (I). As the low molecular compoundhaving a phenolic hydroxyl group represented by the above-describedgeneral formula (I) is low molecular, it is used favorably and suitablyin the photosensitive resin composition of the present invention forcontrolling a dissolution rate as a dissolution promoter or forcontrolling or improving a sensitivity of a photosensitive resincomposition. The controlling of the dissolution rate or the sensitivitycan be made by controlling an amount of these phenolic compounds added.When improving a dissolution rate or a sensitivity, the quantity of thephenolic compound added may be increased and when decreasing thedissolution rate or sensitivity, the quantity may be decreased. As theseamounts can be different depending on a resin to be used or themolecular weight thereof, the amount of these phenolic compounds addedmay be chosen an adequate amount according to a resin to be used or themolecular weight thereof. Furthermore by using these phenolic compounds,a low molecular compound is contained, as a result, in a resin componentto be dissolution-inhibited by an azo coupling reaction with aphotosensitizer compared with not using them. Thereby the difference ofa dissolution rate between an exposed area and an unexposed area, i.e.contrast can be made larger to enable to improve a resolution of thephotosensitive resin composition.

The low molecular compound having a phenolic hydroxyl group representedby the above described general formula (I) includes o-cresol, m-cresol,p-cresol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, bisphenol A, B, C, E, For G, 4,4′,4″-methylidyne trisphenol,2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol,4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]-ethylidene]bisphenol,4,4′-[1-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethylidene]bisphenol,4,4′,4″-ethylidyne trisphenol,4-[bis(4-hydroxyphenyl)methyl]-2-ethoxyphenol,4,4′-[(2-hydroxyphenyl)methylene]-bis[2,3-dimethylphenol],4,4′-[(3-hydroxyphenyl) methylene]bis[2,6-dimethylphenol],4,4′-[(4-hydroxyphenyl)methylene]bis[2,6-dimethylphenol],2,2′-[(2-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],2,2′-[(4-hydroxyphenyl)methylene]bis[3,5-dimethylphenol],4,4′-[(3,4-dihydroxyphenyl)methylene]bis[2,3,6-trimethyl phenol],4-[bis(3-cyclohexyl-4-hydroxy-6-methylphenyl)methyl]-1,2-benzenediol,4,6-bis[(3,5-dimethyl-4-hydroxyphenyl)methyl]-1,2,3-benzenetriol,4,4′-[(2-hydroxyphenyl)methylene]bis[3-methylphenol],4,4′,4″-(3-methyl-1-propanyl-3-ylydine)trisphenol,4,4′,4″,4′″-(1,4-phenylenedimethylidine)tetrakis-phenol,2,4,6-tris[(3,5-dimethyl-4-hydroxyphenyl)methyl]-1,3-benzenediol,2,4,6-tris[(3,5-dimethyl-2-hydroxyphenyl)methyl]-1,3-benzenediol,4,4′-[1-[4-[1-[4-hydoxy-3,5-bis[(hydroxy-3-methylphenyl)methyl]phenyl]-1-methylethyl]phenyl]-ethylidene]bis[2,6-bis(hydroxy-3-methylphenyl)methyl]phenol,4,4′-methylenebis[2-[(2-hydroxy-5-methylphenyl)methyl]-6-methylphenol],and so on. The preferable compounds include 4,4′,4″-methylidinetrisphenol, 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol,4,4′-[1-[4-[1-(4-hydroxyphenyl)-1-methylethyl]phenyl]ethylidene]-bisphenol,4,4′-[1-[4-[2-(4-hydroxyphenyl)-2-propyl]phenyl]ethylidene]-bisphenol,4,4′,4″-ethylidine trisphenol,4,4′-methylenebis[2-[(2-hydroxy-5-methylphenyl)methyl]-6-methylphenol],and so on.

Among these low molecular compounds having a phenolic hydroxyl group,compounds represented by the formula (II) or (III) described below arepreferable.

These low molecular compounds having a phenolic hydroxyl group are usedat the dosage of 1 to 20 parts by weight relative to 100 parts by weightof an alkali-soluble resin.

Further in a photosensitive resin composition of the present invention,a hardening agent having epoxy groups can be incorporated. Thishardening agent having epoxy groups includes a bisphenol A type epoxyresin, a bisphenol F type epoxy resin, a phenol novolak type epoxyresin, a cresol novolak type epoxy resin, an alicyclic epoxy resin,glycidyl ester type epoxy resin, a glycidyl amine type epoxy resin, anda heterocyclic epoxy resin. Not only above described high molecular typeepoxy resin, but also a diglycidyl ether of bisphenol A or bisphenol Fand so on, which are a low molecular type epoxy compound, can be used asa hardening agent in the present invention. This hardening agent havingepoxy groups is used 0.5 to 10 parts by weight, preferably 1 to 7 partsby weight relative to 100 parts by weight of alkali-soluble resin.

In the photosensitive resin composition of the present invention, theremay be incorporated, if necessary, adhesion aids, surfactants, and soon. Examples of the adhesion aids include alkylimidazolines, butyricacid, alkyl acids, polyhydroxystyrene, polyvinyl methyl ether,t-butylnovolak, epoxysilane, epoxypolymers, silanes, and so on. Further,examples of the surfactants include nonionic surfactants such aspolyglycols and the derivatives thereof, i.e., polypropylene glycol orpolyoxyethylene lauryl ether, and so on; fluorine-containing surfactantssuch as Fluorad (trade name; product of Sumitomo 3M Co., Ltd.), Megafac(trade name; product of Dai-Nippon Ink & Chemicals, Inc.), Surflon(trade name; product of Asahi Glass Company, Ltd.) and organosiloxanesurfactants such as KP341 (trade name; product of Shin-Etsu ChemicalCo., Ltd.).

The photosensitive resin composition of the present invention isprepared by dissolving the above described components at the determineddosage in a solvent. At this time each component may be dissolved inadvance respectively in a solvent and each dissolved component may bemixed and prepared at the determined ratio right before usage. Usuallythe solution of a photosensitive resin composition is provided for itsuse after filtered with 0.2 μm filter, and so on.

The photosensitive resin composition of the present invention is formedto a thin film by the following way, for example and is utilized as aplanarization film or an interlayer dielectric. It means that first thesolution of the photosensitive resin composition of the presentinvention is applied on a substrate, whereupon a circuit pattern or asemiconductor device, and so on are formed, if necessary and a pre-bakeof the substrate is conducted to form a coated film of thephotosensitive resin composition. Next, this substrate is pattern-wiseexposed to light through a determined mask, developed by using an alkalideveloper, and rinsed if necessary to form a thin film positive patternof the photosensitive resin composition.

In the above described formation of a thin film, as a coating method ofthe photosensitive resin composition solution, an optional method can beapplied such as a spin coat method, a roll coat method, a land coatmethod, a spray coat method, a flow spreading coat method, a dip coatmethod, and so on. A radiation to be used for an exposure to light caninclude ultra violet light such as g-line, i-line, and so on, deep ultraviolet light such as KrF eximer laser or ArF eximer laser, and so on,X-ray, electron beams, and so on, for example. Further a developmentmethod includes methods so far applied for a resist development such asa paddle development method, a dipping development method, and aswinging dip development method. A developer includes inorganic alkalissuch as sodium hydroxide, potassium hydroxide, sodium carbonate, andsodium silicate, ammonia, organic amines such as ethylamine,propylamine, diethylamine, diethylamino ethanol, and triethylamine,organic tertiary amines such as tetramethylammonium hydroxide, and soon. And as a developer, organic tertiary amines are preferred.

BEST MODE FOR PRACTICING THE INVENTION

The present invention will now be described more specifically byreference to Examples which, however, are not to be construed to limitthe present invention in any way.

EXAMPLE 1

Preparation of Photosensitive Resin Composition

100 parts by weight of poly(methyl methacrylate-co-2-hydroxypropylmethacrylate-co-methacrylic acid) [the containing ratio of methacrylicacid, 15 mole-%], the weight average molecular weight of which is 25,000as determined by polystyrene standards, 22 parts by weight of theesterified product between the compound represented by theabove-described formula (II) and 1,2-naphthoquinone diazide-5-sulfonylchloride, 10 parts by weight of the phenolic compound represented by theabove-described formula (II), and 3 parts by weight of bisphenol A typeepoxy resin, Epicoat 828 (produced by Yuka-Shell Epoxy Company) weredissolved in a mixed solvent composed of propylene glycol monomethylether acetate and ethyl 2-hydroxypropionate (the mixing ratio is 75:25).Then 300 ppm of Megafac R-08 (produced by Dai-Nippon Chemicals & InksCo., Inc.) was added to the solution in order to prevent a radialwrinkles which was so called “striation” and was formed in the surfaceof a resist film upon a rotational coating. After stirred the solution,the solution was filtrated with 0.2 μm filter to prepare aphotosensitive resin composition of the present invention.

Formation of Thin Film Pattern

The composition was applied on a 4-inch silicon wafer by a rotationalcoating and was baked on a hot plate at 100° C. for 90 seconds to form aresist film of 3.0 μm in thickness. The resist film was exposed withlight through a test pattern which contains line and space patternshaving 1:1 line and space width with various kinds of line widths andcontact hole patterns with a various kind of diameters at an optimalexposure dose by g+h-line stepper made by Nikon Co. (FX-604F), and wasdeveloped at 23° C. for 60 seconds with 0.4 weight-% aqueous solution oftetramethylammonium hydroxide to form line and space patterns with 1:1line and space width and contact hole patterns. Then the 4-inch siliconwafer on which patterns were formed was post-baked by heating at 220° C.for 60 minutes in an oven.

Measurement of Limit of Resolution

By the thin film pattern forming method described above, line and spacepatterns with a various widths were formed. Before post-bake treatment,the patterns were observed by Scanning Electronic Microscope (SEM), anda minimal line and space pattern width which was formed at the optimallight-exposure quantity of 5 μm line and space width was made aresolution.

Evaluation of Heat Resistance

A form deterioration of a contact hole having 10 μm in diameter and holediameter: hole gap being 1:1 before and after post-bake treatment whichwas made at 220° C. for 60 minutes was observed by SEM. And the resultswere evaluated by the way that ◯ was put when no flowing of a patternwas observed and X was put when flowing was observed. The result isshown in Table 1.

Evaluation of Transmittance

After a coated film was formed by conducting the same operation asdescribed above except using a quartz glass substrate instead of a4-inch silicon wafer, a heat treatment was made at 220° C. for 60minutes to obtain a glass substrate having a thin film pattern. And thenthe transmittance of this glass substrate having a thin film pattern at400 nm-wavelength was measured using an ultra violet—visible lightspectrophotometer, CARY4E (Ballian company). The results were evaluatedby the way that ◯ was put when a transmittance was 85% or higher and Xwas put when it was lower than 85%. The result is shown in Table 1.

Evaluation of Applicability

A photosensitive resin composition was applied on a 360×465 mm sizeglass substrate with chromium film by a rotational coating followed bybaking on a hot plate at 100° C. for 90 seconds to obtain a resist filmwith 3 μm thickness. Film thickness distribution of this resist film wasmeasured at 600 points and an evenness of applied film thickness wasevaluated by using an index of standard deviation, σ. At this time ⊚ wasput in the case that a is less than 200 Å, ◯ was put when σ was 200 to300 Å and X was put when σ was greater than 300 Å. The result is shownin Table 1.

Evaluation of Development Residue

A photosensitive resin composition was applied on a 360×465 mm sizeglass substrate with chromium film by a rotational coating followed bybaking on a hot plate at 100° C. for 90 seconds to obtain a resist filmwith 3 μm thickness. The resist film was exposed with light through atest pattern which contains line and space patterns having 1:1 line andspace width with various kinds of line widths and contact hole patternswith various kinds of diameters at an optimal exposure dose by g+h-linestepper made by Nikon Co. (FX-604F), and was developed at 23° C. for 60seconds with 0.4 weight-% aqueous solution of tetramethylammoniumhydroxide to form a hole pattern with 1:1 hole diameter and hole gapratio with 10 μm diameter. This hole part was observed by SEM and anevaluation whether a residue after development remained or not was made.Whereupon, ⊚ was put when no development residue was observed, ◯ was putwhen residue was observed on the area surrounding a pattern, upon aplace and X was put when a plenty number of residues were observed onthe area surrounding a pattern. The result is shown in Table 1.

EXAMPLE 2

The same manner was taken as Example 1 except for using the esterifiedproduct between the compound represented by the formula (III) describedbefore and 1,2-naphthoquinone diazide-5-sulfonyl chloride instead of theesterified product between the compound represented by the formula (II)and 1,2-naphthoquinone diazide-5-sulfonyl chloride, and 10 parts byweight of the compound represented by the formula (III) described beforeinstead of 10 parts by weight of the compound represented by the formula(II). The result in Table 1 was obtained.

EXAMPLE 3

The same manner was taken as Example 1 except for using a mixed solventcomposed of propylene glycol monomethyl ether acetate and propyleneglycol n-butyl ether (the mixing ratio is 75:25) instead of a mixedsolvent composed of propylene glycol monomethyl ether acetate and ethyl2-hydroxypropionate (the mixing ratio is 75:25) and the result in Table1 was obtained.

EXAMPLE 4

The same manner was taken as Example 2 except for using a mixed solventcomposed of propylene glycol monomethyl ether acetate and propyleneglycol n-butyl ether (the mixing ratio is 75:25) instead of a mixedsolvent composed of propylene glycol monomethyl ether acetate and ethyl2-hydroxypropionate (the mixing ratio is 75:25) and the result in Table1 was obtained.

EXAMPLE 5

The same manner was taken as Example 1 except for using a mixed solventcomposed of propylene glycol monomethyl ether acetate and propyleneglycol (a mixing ratio 75:25) instead of a mixed solvent composed ofpropylene glycol monomethyl ether acetate and ethyl 2-hydroxypropionate(the mixing ratio is 75:25) and the result in Table 1 was obtained.

EXAMPLE 6

The same manner was taken as Example 2 except for using a mixed solventcomposed of propylene glycol monomethyl ether acetate and propyleneglycol (the mixing ratio is 75:25) instead of a mixed solvent composedof propylene glycol monomethyl ether acetate and ethyl2-hydroxypropionate (the mixing ratio is 75:2.5) and the result in Table1 was obtained.

COMPARATIVE EXAMPLE 1

The same manner was taken as Example 1 except for using a solventcomposed only of propylene glycol monomethyl ether acetate instead of amixed solvent composed of propylene glycol monomethyl ether acetate andethyl 2-hydroxypropionate (the mixing ratio is 75:25) and the result inTable 1 was obtained. TABLE 1 Resolution Heat- Trans- Appli- Development(μm) resistance mittance cability Residue Example 1 2.2 ◯ ◯ ⊚ ⊚ Example2 2.2 ◯ ◯ ⊚ ⊚ Example 3 2.2 ◯ ◯ ◯ ◯ Example 4 2.2 ◯ ◯ ◯ ◯ Example 5 2.2◯ ◯ ◯ ◯ Example 6 2.2 ◯ ◯ ◯ ◯ Comparative 2.3 ◯ ◯ X X Example 1

From the Table 1 above, it can be known that the applicability anddevelopment residue of the photosensitive resin composition of thepresent invention are improved keeping its resolution, heat-resistanceand light transmittance in a good state by using a mixture of propyleneglycol monomethyl ether acetate and a solvent having smaller vaporpressure at the normal temperature and the atmospheric pressure thanthat of propylene glycol monomethyl ether acetate instead of usingpropylene glycol monomethyl ether acetate alone as a solvent in thephotosensitive resin composition comprising an alkali-soluble resinwhich is an acrylic resin, a photosensitizer containing a quinonediazide group, a phenolic compound represented by the general formula(I) described above, a solvent and if necessary a hardening agent. Inthis connection stability depending on time of the photosensitive resincomposition was good in any cases.

ADVANTAGEOUS EFFECTS OF THE INVENTION

As explained above, by the present invention, a photosensitive resincomposition can be obtained with good stability depending on time, highresolution, high heat-resistance and good light transmittance of thepattern film formed as well as improved applicability and improveddevelopment residue. When the photosensitive resin composition of thepresent invention is used as a material for forming a planarizationfilm, an interlayer dielectric, or the like of a semiconductor devise,an FPD, and so on, as its applicability is good, the FPD panel face withuniform lightness at the time of turning on a light of a panel can beproduced. In addition, when the photosensitive resin composition of thepresent invention is used, no development residue can be formed.Therefore as no pattern opening defect problems would occur at a patternopening part, the semiconductor devices, FPDs, etc. in which occurrencesof wiring contact defect arising from the pattern opening defects arecontrolled can be produced. Consequently the photosensitive resincomposition of the present invention can be particularly preferablyapplied for the materials of these applications wherein high heatresistance, high light transmittance are also required.

Industrial Applicability

The photosensitive resin composition of the present invention can beused suitably as a material for forming an interlayer dielectric or aplanarization film of a semiconductor, a FPD, and so on.

1. A photosensitive resin composition comprising an alkali-solubleresin, a photosensitizer having a quinone diazide group and a solvent,wherein the alkali-soluble resin is an acrylic resin, the solvent is amixture of propylene glycol monomethyl ether acetate and a solventhaving smaller vapor pressure than that of propylene glycol monomethylether acetate under normal temperature and atmospheric pressure, and thephotosensitive resin composition further comprises a phenolic compoundrepresented by the general formula (I):

wherein R₁, R₂, R₃, R₄, R₅, R₆ and R₇ represent independently H, a C₁₋₄alkyl group or

whereupon each of m and n is independently an integer of 0 to 2, each ofa, b, c, d, e, f, g and h is an integer of 0 to 5 satisfying a+b≦5,c+d≦5, e+f≦5 and g+h≦5, and i is an integer of 0 to
 2. 2. Thephotosensitive resin composition according to claim 1, wherein thesolvent having smaller vapor pressure than that of propylene glycolmonomethyl ether acetate under normal temperature and atmosphericpressure is at least one member selected from the group consisting ofethyl 2-hydroxpropionate, propylene glycol n-butyl ether and propyleneglycol.
 3. The photosensitive resin composition according to claim 2,wherein the mixing ratio of propylene glycol monomethyl ether acetateand a solvent that is at least one member selected from the groupconsisting of ethyl 2-hydroxpropionate, propylene glycol n-butyl etherand propylene glycol is from 95:5 to 50:50.
 4. The photosensitive resincomposition according to claim 1, wherein the acrylic resin comprises aconstitutional unit derived from an alkyl (meth)acrylate and aconstitutional unit derived from (meth)acrylic acid.
 5. Thephotosensitive resin composition according to claim 4, wherein theacrylic resin comprises 5 to 30 mole-% of a constitutional unit derivedfrom (meth)acrylic acid.
 6. The photosensitive resin compositionaccording to claim 1, wherein the photosensitizer having a quinonediazide group is a reaction product between the compound of generalformula (I) and a naphthoquinone diazide compound.
 7. The photosensitiveresin composition according to claim 6, wherein the phenolic compoundrepresented by the general formula (I) is a compound represented by theformula (II):


8. The photosensitive resin composition according to claim 1, whichfurther comprises a hardening agent having epoxy groups.
 9. Thephotosensitive resin composition according to claim 1, wherein theacrylic resin has a weight average molecular weight of 20,000 to 40,000as determined by polystyrene standards.
 10. The photosensitive resincomposition according to claim 6, wherein the phenolic compoundrepresented by the general formula (I) is a compound represented by theformula (III):